CN103063652A - Preparation method of voltage-controllable multiplex multichannel sensing paper chip for detecting antibiotic residues by molecular imprinting electroluminescence - Google Patents
Preparation method of voltage-controllable multiplex multichannel sensing paper chip for detecting antibiotic residues by molecular imprinting electroluminescence Download PDFInfo
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- CN103063652A CN103063652A CN2012105853232A CN201210585323A CN103063652A CN 103063652 A CN103063652 A CN 103063652A CN 2012105853232 A CN2012105853232 A CN 2012105853232A CN 201210585323 A CN201210585323 A CN 201210585323A CN 103063652 A CN103063652 A CN 103063652A
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Abstract
The invention discloses a preparation method of a voltage-controllable multiplex multichannel sensing paper chip for detecting antibiotic residues by molecular imprinting electroluminescence. The preparation method comprises the following steps of self-preparing a transformer and a multiplexer switch, preparing a multichannel printing electrode on paper, preparing a molecular imprinting (MIPs) sol of antibiotic residues, preparing carbon dots and silicon dioxide pellets coated by the carbon dots, preparing a graphene nano-material, and modifying the surface of the multichannel printing electrode on paper by the graphene nano-material, the silicon dioxide pellets coated by the carbon dots and the MIPs sol by an electrode surface modification technology. The preparation method also comprises the following steps that through the modified multichannel printing electrode, a chemiluminescent analyzer, the transformer and the multiplexer switch, antibiotic residues in sample extract are detected. The voltage-controllable multiplex multichannel sensing paper chip has strong singularity, high sensitivity reaching the ng grade and a low cost, can be operated fast and simply, and realizes automatic reactions and result recording by apparatuses.
Description
Technical field
The present invention relates to the antibiotics leftover detection technical field, more specifically say the preparation of the hyperchannel sensing refill sheet of the controlled and multipath conversion of the residual voltage of a kind of molecular engram electroluminescence detection of antibiotics, the invention still further relates to the method that adopts described electroluminescence sensor to detect the antibiotic residues in breast, meat, the egg products.
Background technology
Microbiotic is that microorganism has other microorganisms in metabolic process and kills or inhibiting secondary metabolite, from the fifties in last century, begin to be commonly used in livestock and poultry breeding industry, its main application comprises Animal diseases treatment, regulant for animal's growth and improves food utilization efficiency etc.Development to livestock and poultry breeding industry plays an important role microbiotic as medicine and non-medicine, in the use amounts of a lot of countries also in continuous increase.After using microbiotic sizable contribution has been made in the development of animal husbandry, but all brought danger thereupon also for breast, meat, egg products processing industry and consumption, the edible antibiotic breast, meat, egg products of containing has sensitization, produces chemical sproof risk the people, and be unfavorable to health.
Along with people to breast, meat, egg products by the transformation of demand type to mass type, the antibiotic residue in breast, meat, the egg products also becomes the focus that the whole world is paid close attention to gradually.Except the supervision and management that strict control microbiotic uses, also must constantly study new detection method.
Set up the method for a kind of high sensitivity and specific fast detecting antibiotic residues, just become current this research field and need one of problem of solution badly.Present existing antibiotic residue object detecting method mainly comprises high performance liquid chromatography, UV-VIS spectrophotometry, fluorescence method, Liquid Chromatography-Mass Spectrometry, enzyme-linked immunosorbent assay and microbial method etc., but these detections or screening methods Shortcomings.
High performance liquid chromatography detection of antibiotics residue be most domestic testing agency all in the method for using, although highly sensitive, the shortcoming such as have the determination relative complex, sense cycle is long, program is complicated, required reagent is various.
2. UV-VIS spectrophotometry and fluorescence method have the advantages such as simple to operate, that cost is low, the range of linearity is wide, but its sensitivity and selectivity are not high.
3. the Liquid Chromatography-Mass Spectrometry remolding sensitivity is higher, but instrument is expensive, the operation more complicated.
4. enzyme-linked immunosorbent assay is highly sensitive, but the operation steps more complicated, but reagent is expensive, cost compare is high.
5. microbial method has low, the advantage such as save time of cost, but generally only is applied to screening experiment.
Above several method is for the determination and analysis of antibiotic residues, generally all exist testing cost high, as a result false positive, testing process is complicated, cost is high, reagent dosage is large, be unsuitable for field quick detection, coexisting substances disturbs the shortcomings such as large, so can not satisfy the needs of actual detection.
Summary of the invention
The technical problem to be solved in the present invention provided a kind ofly have that sample preparation is simple, detection speed is fast, cost is low, voltage that the molecular engram electroluminescence detection of antibiotics of the characteristics such as highly sensitive, high specificity is residual is controlled and the hyperchannel sensing refill sheet of multipath conversion.
In order to solve the problems of the technologies described above, the present invention realizes by following measures: the preparation of the hyperchannel sensing refill sheet of the controlled and multipath conversion of the residual voltage of a kind of molecular engram electroluminescence detection of antibiotics is characterized in that may further comprise the steps:
(1). preparation voltage device (such as accompanying drawing 1) and multiplexer switch (such as accompanying drawing 2);
(2). print electrode on the preparation hyperchannel paper: use first the wax printer at A4 paper printing wax pattern as shown in Figure 3, and will be placed into the A4 paper of wax pattern in panel heater or the baking oven, 60-150 ℃ degree centigrade of lower heating 0.5-2 minute, make wax melt and soak into the thickness of whole paper, form hydrophobic region; Adopt method for printing screen, at zone printing carbon working electrode and the Ag/AgCl contrast electrode (such as accompanying drawing 4) of not printing wax of the A4 paper of handling well;
(3). selection can with the function monomer of antibiotic residues Synthesis of Molecular Imprinting Polymers (Molecularly Imprinted Polymers, be called for short MIPs);
(4). by certain mol proportion template molecule, function monomer, crosslinking chemical, pore-foaming agent, initiating agent and the silicon source of residual antibiotic mixed and to make MIPs colloidal sol;
(5). the preparation Graphene;
(6) preparation carbon point;
(7). the silicon dioxide microsphere that preparation carbon point coats;
(8). utilize layer by layer self assembly surface modification technology etc., the silicon dioxide microsphere that Graphene and carbon point are coated and MIPs Sol-Modified on the hyperchannel paper electrode surface, are made hyperchannel molecular engram electroluminescence sensor on the paper to the paper.
The mol ratio in antibiotic residues template molecule of the present invention, function monomer, crosslinking chemical, pore-foaming agent, initiating agent and silicon source is 0.1~1: 1: 0.5~3: 30~45: 0.05~0.2: 5~15.
The silicon dioxide microsphere that Graphene of the present invention, carbon point coat and molecularly imprinted polymer (MIPs) modify that the multi-channel electrode surface may further comprise the steps on the paper:
(1) hyperchannel on the prepared paper is printed electrode with agate hammer 2 min that carefully polish;
(2) with the ultrasonic dispersion treatment of Graphene, the graphene solution that preparation disperses;
The paper electrode surface of (3) step (1) being processed drips the 10 μ L graphene solutions of processing through step (2), and dries;
(4) ultrasonic processing 10-40 min of silicon dioxide microsphere that the carbon point for preparing coated, the silicon dioxide microsphere solution that the carbon point that obtains disperseing coats;
(5) electrode of processing in the step (3) drips the silicon dioxide microsphere solution of the carbon point coating of processing through step (4), dries;
(6) working electrode surface that dries in the step (5) is dripped the MIPs solution that 10 μ L prepare, then working electrode is used eluant, eluent wash-out 20-30 min, at room temperature dry 5-10 min.
The present invention is further comprising the steps of:
After hyperchannel molecular engram electroluminescence sensor is placed 24 h on the paper, use.
Eluant, eluent of the present invention is acetonitrile or methyl alcohol-acetic acid.
The battery that uses in the transformer of the present invention is the 3V lithium battery.
Chemiluminescent analyzer of the present invention is the auspicious IFFM-E type Flow Injection Analysis/Chemiluminescence instrument advanced in years in Xi'an.
Function monomer of the present invention is diethylaminoethyl methacrylate (DEAEM), α-methacrylic acid (MAA); Described crosslinking chemical is ethylene glycol dimethacrylate (EGDMA); Described initiating agent is azoisobutyronitrile (ABIN); Described pore-foaming agent adopts chloroform, methyl alcohol; The silicon source is ethyl orthosilicate (TEOS).
The preparation of the hyperchannel sensing refill sheet of the controlled and multipath conversion of a kind of molecular engram electroluminescence voltage that detects the antibiotic residues in breast, meat, the egg products, it is characterized in that comprising the steps: that the molecular engram electroluminescence that will make by above-mentioned any one method detects the hyperchannel sensing refill sheet fiting chemical luminescence analyzer of the controlled and multipath conversion of trace antibiotic residue thing voltage, the antibiotic residues in breast, meat, the egg products is carried out highly sensitive, fast detection.
Beneficial effect of the present invention:
1. the preparation of the hyperchannel sensing refill sheet of the controlled and multipath conversion of the residual voltage of a molecular engram electroluminescence detection of antibiotics will make transformer and be introduced in the pick-up unit as power, reduce the cost of detection trace antibiotic residue thing.
2. adopt hyperchannel paper top electrode replacement glass-carbon electrode traditionally, realized the once purpose of experiment detection multiple antibiotic residues thing, shortened detection time, reduced testing cost.
3. the nano-synergistic effect with the graphene nano material is incorporated in the modification of electrode, so that the electrode that prepared molecularly imprinted polymer is modified has higher sensitivity and sensing range.
4. surface modification technology is applied in the preparation process of molecularly imprinted polymer modified electrode, so that the preparation of the molecular engram electroluminescence sensor of nano-synergistic has controllability, has improved sensitivity and the accuracy of experiment.
5. the hyperchannel sensing refill sheet of the controlled and multipath conversion of the residual voltage of the resulting a kind of molecular engram electroluminescence detection of antibiotics of the present invention can be realized hyperchannel, high specific, high sensitivity, low cost, the fast detecting of antibiotic residues in the sample.
6. the high specificity of the hyperchannel sensing refill sheet of the controlled and multipath conversion of the residual voltage of the resulting a kind of molecular engram electroluminescence detection of antibiotics of the present invention, in the sample other non-specific molecules on testing result without impact; Highly sensitive, can reach the ng level; Detection speed is fast, finishes the time that a basic testing process only needs 2-3 min, can realize at short notice the high flux screening of great amount of samples, and reagent dosage is few, and detecting a sample only needs tens microlitre reagent; Cost is low, detects 1 sample and only needs several sharing money.
7. the preparation method of the hyperchannel sensing refill sheet of the controlled and multipath conversion of the residual voltage of a molecular engram electroluminescence detection of antibiotics, operation fast, simply, reaction and result finish and record automatically by instrument, avoided the impact of subjective factor, and ensure good repeatability, be convenient to Site Detection.
Description of drawings
Below in conjunction with the drawings and specific embodiments the present invention is done and to describe in further detail.
Accompanying drawing 1 is transformer photo in kind.
Accompanying drawing 2 is multiplexer switch photo in kind.
Accompanying drawing 3 is the A4 paper printing hydrophobic pattern of waxing.
Accompanying drawing 4 is for printing multi-channel electrode (A, B can detect in two zones different component, also can detected components) on the paper.
Accompanying drawing 5 is the transformer circuit synoptic diagram, its principle of work is: the lithium battery that meets a 3V between VH and VL, by button the voltage that digital regulation resistance will be exported is set, shows by three charactrons, X9313 produces the voltage that will export by single chip computer AT mega8L control.
Three keypress functions are as follows:
K1: arrange; K2: "+"; K3: "-".
This device comprises three charactrons, is respectively D1, D2, D3, is responsible for voltage and shows that the original state charactron is shown as 0.50, and unit is volt, and concrete operations are described as follows:
(1) press " setting " button, enter voltage state is set, press "+" or "--", this magnitude of voltage adds 1 or subtract 1;
(2) first settings are finished, and press " setting " button, and second charactron flicker enters the second setting, and be the same;
After (3) three charactron settings are finished, press " setting " button, charactron stops flicker, and output arranges magnitude of voltage.
Embodiment
Embodiment 1(chloromycetin is such as chloromycetin)
A kind of molecular engram electroluminescence detects the preparation method of the hyperchannel sensing refill sheet of the controlled and multipath conversion of the voltage of residual chloromycetin, may further comprise the steps:
(1). preparation voltage device and multiplexer switch;
(2). print electrode on the preparation hyperchannel paper: use first the wax printer at A4 paper printing wax pattern as shown in Figure 3, and will be placed into the A4 paper of wax pattern in panel heater or the baking oven, 60-150 ℃ degree centigrade of lower heating 0.5-2 minute, make wax melt and soak into the thickness of whole paper, form hydrophobic region; Adopt method for printing screen, at zone printing carbon working electrode and the Ag/AgCl contrast electrode (such as accompanying drawing 4) of not printing wax of the A4 paper of handling well;
(3). selection can be synthesized with chloromycetin the function monomer diethylaminoethyl methacrylate (DEAEM) of MIPs;
(4). template molecule chloromycetin, function monomer diethylaminoethyl methacrylate (DEAEM), crosslinking chemical ethylene glycol dimethacrylate (EGDMA), pore-foaming agent methyl alcohol, initiating agent azoisobutyronitrile (ABIN), silicon source ethyl orthosilicate (TEOS) is 0.1: 1: 0.5 in molar ratio: mix at 30: 0.05: 5, obtain chloromycetin MIPs colloidal sol;
(5). Graphene preparation: under the condition of ultrasonic agitation, in the dispersion liquid of graphene oxide, add the reductive agent hydrazine hydrate, obtain stable graphene suspension;
(6) get the Graphene for preparing, in the cyclopentanone solvent, ultrasonic 30 min obtain preferably Uniform Dispersion graphene solution of stability;
(7) working electrode is selected and is printed multi-channel electrode on the paper, and hyperchannel on the prepared paper is printed electrode with agate hammer 2 min that carefully polish;
The paper electrode surface of (8) step (7) being processed drips the 10 μ L graphene solutions of processing through step (6), and dries;
(9) preparation carbon point material: in an electrolytic cell take carbon-point as working electrode, the Ag/AgCl electrode is contrast electrode, platinum guaze is to electrode, in pH 7.0 sodium dihydrogen phosphates-disodium hydrogen phosphate buffer solution, utilize electrochemical workstation to apply (3.0) V-(+3.0) V voltage (sweeping fast 100 mV/S), scan 10 min;
(10) silicon dioxide microsphere of preparation carbon point coating: 0.04 g SiO
2Microballoon is dissolved in the 4 mL second alcohol and waters (volume ratio 1:1), adds 0.8 mL (3-aminopropyl)-triethoxy-silane magnetic stirring 6 hours, obtains amido modified SiO 4 times with the ethanol centrifuge washing
2Microballoon is with prepared amido modified SiO
2The carbon point solution that microballoon and 1.0 mL are prepared and 1.0 mL N-(3-dimethyl aminopropyl)-N '-ethyl carbodiimide are mixed in that magnetic stirring reacts 12 h in 4 ℃ of environment, and centrifuge washing obtains the SiO that carbon point coats for 5 times
2Microballoon;
(11) electrode of processing to step (8) drips the SiO of the carbon point coating of processing through step (10)
2Microspheres solution is dried;
(12) drip the MIPs colloidal sol that 20 μ L steps (4) prepare to the middle electrode of processing of step (11), dry rear eluant, eluent wash-out 20-30 min that use, at room temperature dry 5-10 min; Detecting chloramphenicol molecular imprinting electroluminescence sensor prepares complete;
The detection chloramphenicol molecular imprinting electroluminescence sensor that makes in conjunction with self-control transformer and multiplexer switch and fiting chemical luminescence analyzer, is carried out highly sensitive, fast detection to chloromycetin residual in breast, meat, the egg products.The results are shown in Table 1.Utilize existing high performance liquid chromatography (HPLC) to detect trace amount chloramphenicol is residual in breast, meat, the egg products, the results are shown in Table 1;
Residual voltage hyperchannel sensing refill sheet and the high performance liquid chromatography (HPLC) controlled and multipath conversion of a kind of molecular engram electroluminescence of table 1 the present invention detection of antibiotics detects Contrast on effect to chloromycetin
The result can find out from table 1: the residual voltage of a kind of molecular engram electroluminescence of the present invention detection of antibiotics is controlled compare with existing high performance liquid chromatography (HPLC) with the hyperchannel sensing refill sheet of multipath conversion have the wider range of linearity, higher sensitivity and lower detectability, cost is lower, more convenient operation.
Embodiment 2(quinolones is such as rifampin)
A kind of molecular engram electroluminescence detects the preparation method of the hyperchannel sensing refill sheet of the controlled and multipath conversion of the residual voltage of rifampin, may further comprise the steps:
(1). preparation voltage device and multiplexer switch;
(2). print electrode on the preparation hyperchannel paper: use first the wax printer at A4 paper printing wax pattern as shown in Figure 3, and will be placed into the A4 paper of wax pattern in panel heater or the baking oven, 60-150 ℃ degree centigrade of lower heating 0.5-2 minute, make wax melt and soak into the thickness of whole paper, form hydrophobic region; Adopt method for printing screen, at zone printing carbon working electrode and the Ag/AgCl contrast electrode (such as accompanying drawing 4) of not printing wax of the A4 paper of handling well;
(3). selection can be synthesized with rifampin the function monomer α-methacrylic acid (MAA) of MIPs;
(4). the template molecule rifampin, function monomer diethylaminoethyl methacrylate (DEAEM), crosslinking chemical ethylene glycol dimethacrylate (EGDMA), pore-foaming agent methyl alcohol, initiating agent azoisobutyronitrile (ABIN), silicon source ethyl orthosilicate (TEOS) is 1: 1: 3 in molar ratio: mix at 45: 0.2: 15, obtain rifampin MIPs colloidal sol;
(5). Graphene preparation: under the condition of ultrasonic agitation, in the dispersion liquid of graphene oxide, add the reductive agent hydrazine hydrate, obtain stable graphene suspension;
(6) get the Graphene for preparing, in the cyclopentanone solvent, ultrasonic 30 min obtain preferably Uniform Dispersion graphene solution of stability;
(7) working electrode is selected and is printed multi-channel electrode on the paper, and hyperchannel on the prepared paper is printed electrode with agate hammer 2 min that carefully polish;
The paper electrode surface of (8) step (7) being processed drips the 10 μ L graphene solutions of processing through step (6), and dries;
(9) preparation carbon point material: in an electrolytic cell take carbon-point as working electrode, the Ag/AgCl electrode is contrast electrode, platinum guaze is to electrode, in pH 7.0 sodium dihydrogen phosphates-disodium hydrogen phosphate buffer solution, utilize electrochemical workstation to apply (3.0) V-(+3.0) V voltage (sweeping fast 100 mV/S), scan 10 min;
(10) silicon dioxide microsphere of preparation carbon point coating: 0.04 g SiO
2Microballoon is dissolved in the 4 mL second alcohol and waters (volume ratio 1:1), adds 0.8 mL (3-aminopropyl)-triethoxy-silane magnetic stirring 6 hours, obtains amido modified SiO 4 times with the ethanol centrifuge washing
2Microballoon is with prepared amido modified SiO
2The carbon point solution that microballoon and 1.0 mL are prepared and 1.0 mL N-(3-dimethyl aminopropyl)-N '-ethyl carbodiimide are mixed in that magnetic stirring reacts 12 h in 4 ℃ of environment, and centrifuge washing obtains the SiO that carbon point coats for 5 times
2Microballoon;
(11) electrode of processing to step (8) drips the SiO of the carbon point coating of processing through step (10)
2Microspheres solution is dried;
(12) drip the MIPs colloidal sol that 20 μ L steps (4) prepare to the middle electrode of processing of step (11), dry rear eluant, eluent wash-out 20-30 min that use, at room temperature dry 5-10 min; Detecting rifampin molecular engram electroluminescence sensor prepares complete;
The detection rifampin molecular engram electroluminescence sensor that makes in conjunction with self-control transformer and multiplexer switch and fiting chemical luminescence analyzer, is carried out highly sensitive, fast detection to rifampin residual in breast, meat, the egg products.The results are shown in Table 2.Utilize existing high performance liquid chromatography (HPLC) to detect the trace rifampin is residual in breast, meat, the egg products, the results are shown in Table 2;
Residual voltage hyperchannel sensing refill sheet and the high performance liquid chromatography (HPLC) controlled and multipath conversion of a kind of molecular engram electroluminescence of table 2 the present invention detection of antibiotics detects Contrast on effect to rifampin
The result can find out from table 2: the residual voltage of a kind of molecular engram electroluminescence of the present invention detection of antibiotics is controlled compare with existing high performance liquid chromatography (HPLC) with the hyperchannel sensing refill sheet of multipath conversion have the wider range of linearity, higher sensitivity and lower detectability, cost is lower, more convenient operation.
Claims (10)
1. the preparation of the hyperchannel sensing refill sheet of the controlled and multipath conversion of the residual voltage of a molecular engram electroluminescence detection of antibiotics is characterized in that may further comprise the steps:
(1.1) preparation voltage device and multiplexer switch;
(1.2) print electrode on the preparation hyperchannel paper;
(1.3) select can with the antibiotic residues Synthesis of Molecular Imprinting Polymers function monomer of (Molecularly Imprinted Polymers is called for short MIPs);
(1.4) by certain mol proportion template molecule, function monomer, crosslinking chemical, pore-foaming agent, initiating agent and the silicon source of residual antibiotic mixed and make MIPs colloidal sol;
(1.5) preparation Graphene;
(1.6) preparation carbon point;
(1.7) silicon dioxide microsphere of preparation carbon point coating;
(1.8) utilize layer by layer self assembly surface modification technology etc., the silicon dioxide microsphere that Graphene and carbon point are coated and MIPs Sol-Modified are made hyperchannel molecular engram electroluminescence sensor on the paper to hyperchannel paper electrode surface;
(1.9) mol ratio in animal medicine residue template molecule of the present invention, function monomer, crosslinking chemical, pore-foaming agent, initiating agent and silicon source is 0.1~1: 1: 0.5~3: 30~45: 0.05~0.2: 5~15.
2. the silicon dioxide microsphere that coats of Graphene of the present invention, carbon point and molecularly imprinted polymer (MIPs) modify that the multi-channel electrode surface may further comprise the steps on the paper:
(2.1) hyperchannel on the prepared paper is printed electrode with agate hammer 2 min that carefully polish;
(2.2) with the ultrasonic dispersion treatment of Graphene, the graphene solution that preparation disperses;
The paper electrode surface of (2.3) step 2.1. being processed drips the 10 μ L graphene solutions of processing through step 2.2., and dries;
(2.4) ultrasonic processing 10-40 min of silicon dioxide microsphere that the carbon point for preparing coated, the silicon dioxide microsphere solution that the carbon point that obtains disperseing coats;
(2.5) electrode of processing in the step 2.3. drips the silicon dioxide microsphere solution that the carbon point processed through step 2.4. coats, and dries;
(2.6) working electrode surface that dries among the step 2.5. is dripped the MIPs solution that 10 μ L prepare, then working electrode is used eluant, eluent wash-out 20-30 min, at room temperature dry 5-10 min;
(2.7) the molecular engram electroluminescence sensor for preparing among the step 2.6. is placed cooperated behind 24 h self-control transformer, multiplexer switch and chemiluminescent analyzer that antibiotic residues is detected.
3. described molecular engram electroluminescence sensor according to claim 1-2, it is characterized in that: described carbon point material preparation process is: in an electrolytic cell take carbon-point as working electrode, the Ag/AgCl electrode is contrast electrode, platinum guaze is to electrode, in pH 7.0 sodium dihydrogen phosphates-disodium hydrogen phosphate buffer solution, utilize electrochemical workstation to apply (3.0) V-(+3.0) V voltage (sweeping fast 100 mV/S), scan 10 min.
4. described molecular engram electroluminescence sensor according to claim 1-3 is characterized in that: the preparation process of the silicon dioxide microsphere of preparation carbon point coating is: 0.04 g SiO
2Microballoon is dissolved in the 4 mL second alcohol and waters (volume ratio is 1:1), adds 0.8 mL (3-aminopropyl)-triethoxy-silane magnetic stirring 6 hours, obtains amido modified SiO 4 times with the ethanol centrifuge washing
2Microballoon is with prepared amido modified SiO
2The carbon point solution that microballoon and 1.0 mL are prepared and 1.0 mL N-(3-dimethyl aminopropyl)-N '-ethyl carbodiimide are mixed in that magnetic stirring reacts 12 h in 4 ℃ of environment, and centrifuge washing obtains the SiO that carbon point coats for 5 times
2Microballoon.
5. each described molecular engram electroluminescence sensor according to claim 1-4 is characterized in that: described function monomer is diethylaminoethyl methacrylate (DEAEM), α-methacrylic acid (MAA); Described crosslinking chemical is ethylene glycol dimethacrylate (EGDMA); Described initiating agent is azoisobutyronitrile (ABIN); Described pore-foaming agent adopts chloroform, methyl alcohol; The silicon source is ethyl orthosilicate (TEOS).
6. each described molecular engram electroluminescence sensor according to claim 1-5, it is characterized in that: the mol ratio in described template molecule, function monomer, crosslinking chemical, initiating agent, pore-foaming agent and silicon source is 0.1~1: 1: 0.5~3: 30~45: 0.05~0.2: 5~15.
7. each described molecular engram electroluminescence sensor according to claim 1-6, it is characterized in that: described eluant, eluent is acetonitrile or methyl alcohol-acetic acid.
8. each described molecular engram electroluminescence sensor according to claim 1-7 is characterized in that: used battery is 3 V lithium batteries in the self-control transformer.
9. each described molecular engram electroluminescence sensor according to claim 1-8 is characterized in that: described chemiluminescent analyzer is the auspicious IFFM-E type Flow Injection Analysis/Chemiluminescence instrument advanced in years in Xi'an.
10. each described molecular engram electroluminescence sensor according to claim 1-9 is characterized in that: the control panel surface of self-control transformer is comprised of three operating keys and three figure place code display tubes.
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104530334A (en) * | 2015-01-09 | 2015-04-22 | 江苏大学 | Preparation method and application SiO2/GO surface metal ion imprinted polymer |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001002839A1 (en) * | 1999-07-05 | 2001-01-11 | Novartis Ag | Sensor platform, apparatus incorporating the platform, and process using the platform |
US20030129092A1 (en) * | 1998-04-28 | 2003-07-10 | Murray George M. | Molecularly imprinted polymer solution anion sensor |
CN101581673A (en) * | 2009-06-04 | 2009-11-18 | 江南大学 | Sensor based on iridium composition electroluminescence and molecular imprinting recognition technology |
CN102121903A (en) * | 2010-12-03 | 2011-07-13 | 江南大学 | Sensor for detecting drugs by molecular imprinting (MI)-electrochemiluminescence (ECL) method |
-
2012
- 2012-12-31 CN CN201210585323.2A patent/CN103063652B/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20030129092A1 (en) * | 1998-04-28 | 2003-07-10 | Murray George M. | Molecularly imprinted polymer solution anion sensor |
WO2001002839A1 (en) * | 1999-07-05 | 2001-01-11 | Novartis Ag | Sensor platform, apparatus incorporating the platform, and process using the platform |
CN101581673A (en) * | 2009-06-04 | 2009-11-18 | 江南大学 | Sensor based on iridium composition electroluminescence and molecular imprinting recognition technology |
CN102121903A (en) * | 2010-12-03 | 2011-07-13 | 江南大学 | Sensor for detecting drugs by molecular imprinting (MI)-electrochemiluminescence (ECL) method |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104530334A (en) * | 2015-01-09 | 2015-04-22 | 江苏大学 | Preparation method and application SiO2/GO surface metal ion imprinted polymer |
CN104926981A (en) * | 2015-05-07 | 2015-09-23 | 天津科技大学 | Preparation method for fluorescence sensing material based on molecular imprinting and carbon dots |
CN108084337A (en) * | 2017-12-06 | 2018-05-29 | 华中科技大学 | The double imprinted materials of the paper substrate of Selective recognition protein and preparation method and application |
CN108084337B (en) * | 2017-12-06 | 2019-06-07 | 华中科技大学 | The double imprinted materials of the paper base of Selective recognition protein and preparation method and application |
CN108636467A (en) * | 2018-05-22 | 2018-10-12 | 福州大学 | A kind of three-dimensional paper substrate chip of stannic oxide/graphene nano piece enhancing and its application |
CN108636467B (en) * | 2018-05-22 | 2023-04-07 | 福州大学 | Graphene oxide nanosheet enhanced three-dimensional paper-based chip and application thereof |
CN109092381A (en) * | 2018-11-20 | 2018-12-28 | 中国科学院烟台海岸带研究所 | A method of paper chip is prepared based on aqueous polyurethane acrylate |
CN110887883A (en) * | 2019-12-05 | 2020-03-17 | 吉林大学 | Electrochemical method for rapidly detecting penicillin sodium based on magnetic material |
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